Arylamide



Patented Mar. 1 2, 1940 PATENT OFFICE,

AR'YLAMIDE Friedrich Muth, Leverkusen I. G.-Werk, Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application April 3, 1939, Serial No. 265,770. In Germany April 12, 1937 Claims.

The present invention relates to new intermediates suitable for the manufacture of waterinsoluble azodyestuffs and to a method of preparing these products; more particularly it re- 5 lates to amides of 3-hydroxy-fluorene-2-carboxylic acids.

My new intermediates are obtainable by converting 3-hydroxy-fluorene-2-carboxylic acids, having a free 4-p0siti0n, or the functional del0 rivatives thereof into the amides of aromatic or heterocyclic monoor diamines. This can be effected by starting from the halides or esters of the said carboxylic acids and causing the same to react with aromatic or heterocyclic monoor diamines or by reacting aromatic or heterocyclic isocyanic acid esters with the 3-hydroxy-fiuorene-2-carboxylic acids. The 3-hydroXy-flu0- rene-Z-carboxylic acids which serve as starting materials for the above process can be obtained according to my'copending application Ser. No. 200,128, filed April 5, 1938.

The new amides may be substituted in that benzene nucleus of the fluorene which does not bear the hydroxy group and the carboxylic acid amide group and also at the carbon atom in the 9-position. As substituents may be mentioned alkyl, alkoxy, nitro, halogen, trifluoromethyl, phenylamino, alkyl-sulione, aralkylsulfone, arylsulfone, alkyl-C'0-, aryl-CO- and so on; also a further nucleus may be condensed to the mentioned benzene nucleus of the fluorene, forming in this way, for instance, a naphthalene ring system or if the nucleus condensed to the fluorene is hydrogenated, a tetrahydronaphthalene ring system. Such substituted amides can be obtained from the following 3-hydroxy-fluorene-2- carboxylic acids; the methyl-3-hydroxy-fluorene-Z-carboxylic acids, the chloro-3-hydroxyfluorene-Z-carboxylic acids, the methoxy-3-hydroxy-fluorene-Z-carboxylic acids, which bear the substituent inquestion in one of the positions 5, 6, 7 or 8 and also from the 3-hydroxy-fluorene- Z-carboxylic acids substituted in the 9-position;

. funther the benzo-3-hydroxy-fluorene-2-carboxylic acids having the benzene nucleus condensed to the positions 5.6, 6.7 or 7.8 and also the corresponding tetrahydro-acids.

My new amides show in comparison with other amides derived from multinuclear 'o-hydroxy carboxyllc acids a good solubility; thus they dissolve in general in hot aqueous lyes. They are distinguished by a very good affinity towards cellulosic fibers and by a good coupling energy and are, therefore, suitable for the manufacture of water-insoluble azo-dyestuffs according to the ice-color method.

This application is in part a continuationof my copending application Ser. No. 200,076, filed April 5, 1938. I

The following examples illustrate the inven- "10' tion, without, however, restricting it thereto, the parts being by weight:

Examples 226 parts of 3-hydroxy-fluorene 2-carboxylic 15 acid and 123 parts of Z-anisidin'e are suspended in toluene. parts of phosphorus trichloride are dropped in at 60 C. and the whole is heated to boiling until the formation of hydrochloric acid has terminated. Sodium carbonate solution 20 is added to the reaction mixture until it has assumed a strongly alkaline reaction and the toluene is then removed by evaporation. The residue is purified by dissolving it with dilute caustic soda lye and precipitating with acid. By crystallization from alcohol or toluene the new arylide of the formula -OH GONE is obtained in. short monosymmetrical prisms having a melting point of 176-177 C,

The arylamide obtained in an analogous manner with 1-amino-2.5-dimethoxybenzene has the following formula: 40

WOW 0H,

CONE- and crystallizes from toluene in yellow needles of M. P. l86-187 C.

In the following table the melting points are 5 given of further amides of 3-hydr0Xy-fiuorene- 2-carboxylic acid with amines such as Melting point, C.

Aniline 246 2-toluidine 211 3-toluidine 232 4-toluidine 265 Z-aminoethylbenzene 168 3-anisidine 213 4-anisidine 263 2-phenetidine 168 3-ch1oroaniline 233 4-chloroaniline 284 3-fluoroaniline 244 3-aminobenzotrifiuoride 225 4-aminophenyltrifiuoro-rnethy1sulfone 278 3-nitroaniline 288 1-amino-2.3-dimethylbenzene 230 1-amino-2.4-dimethylbenzene 206 1-amino-2.5-dimethylbenzene 169 1-amino-3.4-dimethylbenzene 227 1an1ino-3.E-dimethylbenzene 207 1-amino-2-methyl-4-methoxybenzene 228 1-amino-2-methyl-5-methoxybenzene 1-amino-3-methyl-4-methoxybenzene 209 1-amino-3-methyl-6-methoxybenzene 210 1-amino-4-methyl3-*nethoxybenzene 202 1-amino-2-methyl-4-ohlorobenzene 236 l-amino-Z-methyl-5-chlorobenzene 238 1-amino-2.4-dimethoxybenzene 153 1-amino-3.5-dicyanobenzene 265 1-amino-2-methoxy-4-chlorobenzene 232 l -amino-2-methoxy-5-chlorobenzene 215 1-amino-4-methoxy-3-chlorobenzene- 230 l -amino2-methoxypl1enyl 5 trifiuoromethylsulfone 251-252 l-amino- 2.4 dimethoxy 5 chlorobenzene 249 l-amino 2.4 dimethoxy 5 trifluoro methylbenzene 242 1-amino-2.5-dimethoxy-4-chlorobenzene 232 1 -amino-2-methoXy-5-methyl 4 chlorobenzene 212 1-amino-4-ch1oro 2 trifiuoro-methylbenzene 216 l-amino-Z-chloro 5 trifluoro-methylbenzene 238 l-amino-Z-bromo 5 trifluoro-methylbenzene 243 l-amino-Z-nitro 4 trifiuoro methylbenzene 280 l-amino-Z-nitro 5 trifluoro methylbenzene 291 l-amino-3-chloro 5 trifiuoro-methylbenzene 203-204 1-amino- 3.5 di-trifluoro methylben zene 224 l-naphthylamine 221 2-naphthylamine 270 a-tetrahydronaphthylamine 205 2-an1ino-3-methoxy-diphenylene-oxide 296 Dianisidine(with 2 mols acids) more than 300 In the same way the amides of substituted 3- hydroxy-fiuorene-2-carboxylic acids are obtained. 6-methyl-3-hydroxy-fiuorene 2 carboxylic acid yields with 2-anisidine the product of the following formula:

O0.NE

OCH:

which melts at 172 amides with C. The corresponding 2-toluidine has the melting point.- 21'7 1-amino-2.5-dimethoxybenzene 'do 189 1-amino2.5-dimethoxy-4-chlorobenzene do 206 and the 9-methyl-3-hydroxy-fluorene-2-carboxylic acid yields with 1-amino-2.5-dimethoxyben- Zene the product of the formula:

above Grignards reaction instead of methylmagnesium bromide aryl-, aralkylor other alkyl-niagnesium halides are used the corresponding 9-aryl- -aralkylor -alkylfluorene derivatives are obtained. According to known methods also the corresponding 9.9-disubstituted derivatives can be prepared.

The 6ch.loro-3-hydroXy-fiuorene-2-carboxylic acid yields with o-toluidine the ai'ylide of the formula:

melting at 240 C. Additional arylides of this acid are made with C. 2-anisidine melting point 188 l-amino-2-methyl-4methoxybenzene do 259 S-amino-benzotrifiuoride do 215 1amino-3.5-di-trifluoro-methylbenzene do 219 The 6-chloro-3hydroXy-fluorene from which the 6-cl1loro-3-hydroxy-f1uorene-2-carboxylic acid (colorless needles from butylalcohol M. P. 293 C.) is obtained, is prepared as follows: 4- chloro-2-amino-benzoic acid is acted upon with benzene-sulfochloride to 2-benzene-sulfamino-4- chloro-benzoic acid (white needles from glacial acetic acid M. P. 188-189 C.), converted into 2- benzene-suifamino-4-chlorobenzoyl c h l o r i d e (white needles from chloroform M. P. -181" C.), condensed with anisol to 2-benzene-sulfamino-4-chloro-4'-methoxy-b e n z o p h e n on e (compact prisms from toluene M. P. l39-l40 C.), saponified, diazotized and condensed (ringformation) to 6-chloro-3-methoxy-fiuorenone (fine yellow needles from alcohol M. P. 178 0.), reduced to 6-chloro-3-methoXy-fiuorene (nacreous scales M. P. 105 C.) and demethylated to 6- chloro-3-hydroXy-fluorene (White needles from toluene M. P. 159-160 C.)

From the '7-chloro-3-hydroxy-fiuorene-2-carboxylic acid may be mentioned the 1-('7-chloro- 3 hydroxy-fluorene-2-carboylamino)-2.5 dimethoxy-benzene of the formula:

OH O CH! Cl- CO.NH

melting at 215 C. The '7-chloro-3-hydroxyfluorene-Z-carboxylic acid (white needles M. P. 293 C.) is obtained from the 'Z-chloro-B-hydroxy-fiuorene which latter is prepared in a similar way as the 6-chloro-product: 5-chloro-2- amino benzoic acid 2 benzene-sulfamino-5- chloro-benzoic acid (colorless prisms from benoorn which melts at 210 0., with 1-amino-2.5-dimethoxybenzene an amide of the melting point 230 C.

I claim: 1. As new products arylamides of the general formula 0 CO.NH.R

wherein X stands for one of the group consisting of the benzene nucleus, the naphthalene nucleus, and the alkyl and halogen substitution products thereof, Y and Z stand for radicals of the group consisting of hydrogen, alkyl, aralkyl and aryl, and R stands for an aromatic radical, being water-insoluble substances.

2. As new products arylamides of the general formula CO.NH.R

wherein X stands for one of the group consisting of the benzene nucleus, the naphthalene nucleus,

and the alkyl and halogen substitution products thereof, and R stands for an aromatic radical, being water-insoluble substances.

3. As a new product the arylamide of the formula CO.NH OOHa OCH:

melting at 153 C.

4. As a new product the arylamide of the formula OH C1 melting at 215 C.

5. As a new product the arylamide of the OH CF;

CO.NH C 2 melting at 203-204 formula FRIEDRICH MUTH. 

